Response surface methodology for the enantioseparation of dinotefuran and its chiral metabolite in bee products and environmental samples by supercritical fluid chromatography/tandem mass spectrometry

• Response surface optimization strategy was introduced for the chiral separation of the enantiomers of dinotefuran and its metabolite.
• Sixteen chiral stationary phases with different co-solvents were evaluated in terms of the resolution and retention of the enantiomers.
• Various extractant and purification sorbents were discussed systematically to obtain acceptable recoveries and high sensitivity.
• Satisfactory validation criteria and successful application to real samples were demonstrated.

Tracing the enantiomers of dinotefuran and its metabolite in bee products and relevant environmental matrices is vital because of the high toxicity of their racemates to bees. In this study, a statistical optimization strategy using three-dimensional response surface methodology for the enantioseparation of dinotefuran and its metabolite UF was developed by a novel supercritical fluid chromatography/tandem mass spectrometry (SFC–MS/MS) technique. After direct evaluation of the chromatographic variables – co-solvent content, mobile phase flow rate, automated backpressure regulator pressure (ABPR), and column temperature – involved in the separation mechanism and assessment of the interactions among these variables, the optimal SFC–MS/MS working conditions were selected as a CO2/2% formic acid-methanol mobile phase, 1.9 mL/min flow rate, 2009.8 psi ABPR, and 26.0 °C column temperature using an amylose tris-(3,5-dimethylphenylcarbamate) chiral stationary phase under electrospray ionization positive mode. Baseline resolution, favorable retention, and high sensitivity of the two pairs of enantiomers were achieved in pollen, honey, water, and soil matrices within 4.5 min. Additionally, the parameters affecting the dispersive solid-phase extraction procedure, such as the type and content of extractant or purification sorbents, were systematically screened to obtain better extraction yields of the enantiomers. Mean recoveries were between 78.3% and 100.2% with relative standard deviations lower than 8.0% in all matrices. The limits of quantification ranged from 1.0 μg/kg to 12.5 μg/kg for the dinotefuran and UF enantiomers. Furthermore, the developed method was effectively applied to authentic samples from a market, an irrigation canal, and a trial field, and the enantioselective dissipation of dinotefuran and UF in soil was demonstrated.